Problem-driven scenario generation: an analytical approach for stochastic programs with tail risk measure

Mathematical Programming - Scenario generation is the construction of a discrete random vector to represent parameters of uncertain values in a stochastic program. Most approaches to scenario...     

Understanding the electron-stimulated surface reactions of organometallic complexes to enable design of precursors for electron beam-induced deposition

Standard practice in electron beam-induced deposition (EBID) is to use precursors designed for thermal processes, such as chemical vapor deposition (CVD). However, organometallic precursors that yield pure metal deposits in CVD often create EBID deposits with high levels of organic contamination. This contamination negatively impacts the deposit’s properties (e.g., by increasing resistivity or decreasing catalytic activity) and severely limits the range of potential applications for metal-containing EBID nanostructures. To provide the information needed for the rational design of precursors specifically for EBID, we have employed an ultra-high vacuum (UHV) surface science approach to identify the elementary reactions of organometallic precursors during EBID. These UHV studies have demonstrated that the initial electron-induced deposition of the surface-bound organometallic precursors proceeds through desorption of one or more of the ligands present in the parent compound. In specific cases, this deposition step has been shown to proceed via dissociative electron attachment, involving low-energy secondary electrons generated by the interaction of the primary beam with the substrate. Electron beam processing of the surface-bound species produced in the initial deposition event usually causes decomposition of the residual ligands, creating nonvolatile fragments. This process is believed to be responsible for a significant fraction of the organic contaminants typically observed in EBID nanostructures. A few ligands (e.g., halogens) can, however, desorb during electron beam processing while other ligands (e.g., PF₃, CO) can thermally desorb if elevated substrate temperatures are used during deposition. Using these general guidelines for reactivity, we propose some design strategies for EBID precursors. The ultimate goal is to minimize organic contamination and thus overcome the key bottleneck for fabrication of relatively pure EBID nanostructures.     

Development of a selective chemical etch to improve the conversion efficiency of Zn-rich Cu2ZnSnS4 solar cells

Improvement of the efficiency of Cu(2)ZnSnS(4) (CZTS)-based solar cells requires the development of specific procedures to remove or avoid the formation of detrimental secondary phases. The presence of these phases is favored by the Zn-rich and Cu-poor conditions that are required to obtain device-grade layers. We have developed a selective chemical etching process based on the use of hydrochloric acid solutions to remove Zn-rich secondary phases from the CZTS film surface, which are partly responsible for the deterioration of the series resistance of the cells and, as a consequence, the conversion efficiency. Using this approach, we have obtained CZTS-based devices with 5.2% efficiency, which is nearly twice that of the devices we have prepared without this etching process.     

(PbS)32: a baby crystal

Theoretical calculations based on density functional theory have found (PbS)(32) to be the smallest cubic cluster for which its inner (PbS)(4) core enjoys bulk-like coordination. Cubic (PbS)(32) is thus a "baby crystal," i.e., the smallest cluster, exhibiting sixfold coordination, that can be replicated to obtain the bulk crystal. The calculated dimensions of the (PbS)(32) cluster further provide a rubric for understanding the pattern of aggregation when (PbS)(32) clusters are deposited on a suitable surface, i.e., the formation of square and rectangular, crystalline nano-blocks with predictable dimensions. Experiments in which mass-selected (PbS)(32) clusters were soft-landed onto a highly ordered pyrolytic graphite surface and the resulting aggregates imaged by scanning tunneling microscopy provide evidence in direct support of the computational results.     

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Atomic oxygen reactions with semifluorinated and n-alkanethiolate self-assembled monolayers

The interaction of atomic oxygen (O(3P)) with semifluorinated self-assembled monolayers (CF-SAMs), two different n-alkanethiolate self-assembled monolayers, and a carbonaceous overlayer derived from an x-ray modified n-alkanethiolate SAM have been studied using in situ x-ray photoelectron spectroscopy. For short atomic oxygen exposures, CF-SAMs remain intact, an effect ascribed to the inertness of C-F and C-C bonds toward atomic oxygen and the well-ordered structure of the CF-SAMs. Following this initial induction period, atomic oxygen permeates through the CF3(CF2)7 overlayer and initiates reactions at the film/substrate interface, evidenced by the formation of sulfonate (RSO3) species and Au2O3. These reactions lead to the desorption of intact adsorbate chains, evidenced by the loss of carbon and fluorine from the film while the C(1s) spectral envelope and the C(1s)/F(1s) ratio remain virtually constant. In contrast, the reactivity of atomic oxygen with alkanethiolate SAMs is initiated at the vacuum/film interface, producing oxygen-containing carbon functional groups. Subsequent reactions of these new species with atomic oxygen lead to erosion of the hydrocarbon film. Experiments on the different hydrocarbon-based films reveal that the atomic oxygen-induced kinetics are influenced by the thickness as well as the structural and chemical characteristics of the hydrocarbon overlayer. Results from this investigation are also discussed in the context of material erosion by AO in low Earth orbit.     

A Comparison of PE Surfaces Modified by Plasma Generated Neutral Nitrogen Species and Nitrogen Ions

The surface modification of polyethylene (PE) by neutral nitrogen species (ground and excited state N₂ as well as atomic N; modified nitrogen plasma treatment) has been compared to the effect of nitrogen ion bombardment using X-ray Photoelectron Spectroscopy (XPS) and contact angle measurements. XPS results indicate that a greater nitrogen concentration was grafted during the modified nitrogen plasma treatment of PE, an effect that was attributed to surface sputtering during ion beam modification. The distribution of nitrogen-containing functionalities was strongly dependent upon the treatment strategy; the modified nitrogen plasma treatment lead predominantly to imine groups being formed at the PE surface, while amine groups were the dominant species produced during ion beam modification. The presence of electron irradiation during the modified nitrogen plasma treatment of PE did not modify the rate of nitrogen incorporation or change the nature of N-containing functional groups produced but did lead to a systematic decrease in contact angle.     

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): a comparison with CCl4

The kinetics of decomposition and subsequent chemistry of adsorbed CF(2)Cl(2), activated by low-energy electron irradiation, have been examined and compared with CCl(4). These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF(2)Cl(2) and CCl(4) dissociation increase in an H(2)O (D(2)O) environment (2-3x), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H(2)O, using 180 eV incident electrons, are measured (using TPD) to be 1.0+/-0.2 x 10(-15) cm(2) for CF(2)Cl(2) and 2.5+/-0.2 x 10(-15) cm(2) for CCl(4). RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl(-) and F(-) anions in the halocarbon/water films and production of H(3)O(+), CO(2), and intermediate compounds COF(2) (for CF(2)Cl(2)) and COCl(2), C(2)Cl(4) (for CCl(4)) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.     

Phosphorus-functionalized multi-wall carbon nanotubes as flame-retardant additives for polystyrene and poly (methyl methacrylate)

The relationship between the properties with the composition of nickel–aluminium mixed oxides was investigated in this work. Ni–Al materials with Ni/Al molar ratios between 0.5 and 9 were synthesised via co-precipitation. The samples were characterised using the following techniques: surface area measurements (S _BET), thermogravimetry, X-ray diffraction and temperature-programmed reduction, desorption and oxidation (H₂-TPR, NH₃-TPD and TPO/DTA). Samples with Ni/Al ratio = 0.5 primarily formed the Al₂O₃ phase, whereas Ni/Al ratio = 9 mainly led to the bulk NiO phase. However, Ni/Al ratios between 1 and 3 favoured the formation of the mixed oxide phase with increased thermal stability and specific surface area and decreased crystallite sizes. The lower Ni/Al ratios led to the production of ethylene, which is likely related to the higher number of sites with stronger acidity. The samples with Ni/Al ratios of 2 and 3 promoted selectivity towards synthesis gas. For higher Ni/Al ratios, low thermal stability leading to sintering and deactivation due to coke formation was observed.